US7122227B2 - Chiral photoisomerizable compounds - Google Patents

Chiral photoisomerizable compounds Download PDF

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US7122227B2
US7122227B2 US10/432,015 US43201503A US7122227B2 US 7122227 B2 US7122227 B2 US 7122227B2 US 43201503 A US43201503 A US 43201503A US 7122227 B2 US7122227 B2 US 7122227B2
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Julian Vaughn-Spickers
Simon Greenfield
Ian Victor Edward Hassall
Christopher Dunn
Richard Harding
Tony Jenkins
Alison May
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2021—Compounds containing at least one asymmetric carbon atom
    • C09K19/2028—Compounds containing at least one asymmetric carbon atom containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -COO-CH*-CH3
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition

Definitions

  • the invention relates to chiral photoisomerizable compounds, to liquid crystalline mixtures and polymers containing them, and to the use of these chiral photoisomerizable compounds, mixtures and polymers in optical and electrooptical devices like liquid crystal displays or projection systems, optical elements like polarizers, retardation films, compensators, colour filters or holographic elements, in adhesives, synthetic resins with anisotropic mechanical properties, cosmetic and pharmaceutical compositions, diagnostics, liquid crystal pigments, for decorative and security applications, in nonlinear optics, optical information storage or as chiral dopants.
  • Chiral materials which change their chirality upon photoirradiation are known in prior art. For example, photoisomerizable chiral materials were reported which show E-Z or cis-trans isomerization upon photoirradiation and are thereby converted from one chiral form into another chiral form. Further known are photodegradable or (photo)tunable chiral materials (TCM) that change from chiral to achiral or to a racemic mixture upon photoirradiation, due to destruction of their chirality by photoelimination or photocleavage of the chiral center.
  • TCM photodegradable or (photo)tunable chiral materials
  • Photoisomerizable chiral materials have been suggested inter alia for the preparation of cholesteric polymer films with patterned optical properties, which can be used as optical components like colour filters or broadband reflective polarizers in liquid crystal displays.
  • the preparation of patterned cholesteric films is described for example in WO 00/34808.
  • WO 98/57223 discloses a multi-domain liquid crystal display with a nematic liquid crystal material comprising a polymerizable menthone derivative as photoisomerizable chiral dopant.
  • the display comprises different sub-pixels in which the twist sense of the liquid crystal material is mutually opposite. It is manufactured by photoirradiation of a layer of liquid crystalline material containing a photoisomerizable chiral dopant with a given twist sense and a non-isomerizable chiral dopant with opposite twist sense through a photomask. This causes the isomerizable dopant in the exposed parts of the layer to change its chirality, leading to a change of the helical pitch in the exposed parts.
  • U.S. Pat. No. 5,668,614 discloses a multicolour cholesteric display made from a cholesteric liquid crystal mixture comprising a tunable chiral material (TCM).
  • TCM tunable chiral material
  • the display is prepared by partially exposing the liquid crystal mixture with the TCM to photoirradiation through a photomask. This leads to a change of the chirality of the TCM by photocleavage or photoracemisation and thus to a change of the helical pitch in the exposed parts of the cholesteric liquid crystal material. Thereby regions with different pitch and thus different colours of the reflected wavelength are obtained and a multicolour display is realized.
  • TCMs Tunable chiral materials
  • TCMs Tunable chiral materials
  • F. Vicentini, J. Cho and L. Chien, Liq. Cryst. 24 (1998), 483–488 describe binaphthol derivatives as TCMs and their use in multicolour cholesteric displays.
  • HTP helical twisting power
  • HTP 1 p ⁇ c ( 1 ) wherein c is the concentration of the chiral compound and p is the helical pitch.
  • a short pitch can be achieved by using a high amount of the chiral compound or by using a chiral compound with a high absolute value of the HTP.
  • high amounts are needed to induce a short pitch.
  • chiral compounds of prior art Another disadvantage of chiral compounds of prior art is that they often show low solubility in the liquid crystal host mixture, which leads to undesired crystallization at low temperatures.
  • typically two or more different chiral compounds have to be added to the host mixture. This implies higher costs and also requires additional effort for temperature compensation of the mixture, as the different chiral compounds usually have to be selected such that their temperature coefficients of the twist compensate each other.
  • the invention has the aim of providing chiral photoisomerizable compounds having these properties, but not having the disadvantages of the chiral compounds of prior art as discussed above.
  • Another aim of the invention is to extend the pool of chiral photoisomerizable compounds available to the expert.
  • liquid crystalline or mesogenic material or ‘liquid crystalline or mesogenic compound’ should denote materials or compounds comprising one or more rod-shaped, lath-shaped or disk-shaped mesogenic groups, i.e. groups with the ability to induce liquid crystal phase behaviour.
  • Rod-shaped and lath-shaped mesogenic groups are especially preferred.
  • the compounds or materials comprising mesogenic groups do not necessarily have to exhibit a liquid crystal phase themselves. It is also possible that they show liquid crystal phase behaviour only in mixtures with other compounds, or when the mesogenic compounds or materials, or the mixtures thereof, are polymerized.
  • liquid crystal material is used hereinafter for both liquid crystal materials and mesogenic materials
  • meogen is used for the mesogenic groups of the material
  • Materials exhibiting a cholesteric phase or chiral smectic C phase are preferred. Particularly preferred are materials exhibiting a cholesteric phase.
  • film includes self-supporting, i.e. free-standing, films that show more or less pronounced mechanical stability and flexibility, as well as coatings or layers on a supporting substrate or between two substrates.
  • photoisomerizable group means a group that shows isomerization, for example cis-trans or E-Z isomerization, imparting a change in shape upon photoirradiation with a suitable wavelength, preferably in the range from 250 to 400 nm, very preferably from 300 to 400 nm.
  • FIG. 1 depicts the reflection spectrum of polymer films P1–P5 according to example 10, prepared by polymerizing a mixture comprising an inventive photoisomerizable compound after photoisomerization for different periods of time.
  • FIG. 2 depicts the central wavelength of reflection of films P1–P5 versus photoisomerization time.
  • One object of the invention are chiral photoisomerizable compounds of formula I
  • Another object of the invention is a liquid crystalline mixture containing at least one compound of formula I.
  • Another object of the present invention is a polymerizable liquid crystalline mixture comprising at least two compounds, at least one of which is a compound of formula I and at least one of which is a polymerizable compound.
  • Another object of the invention is a chiral linear or crosslinked anisotropic polymer obtainable by polymerizing a polymerizable liquid crystalline mixture comprising one or more compounds of formula I.
  • Another object of the invention is the use of a chiral compound, mixture or polymer as described above in optical and electrooptical devices like liquid crystal displays or projection systems, such as STN, TN, AMD-TN, temperature compensation, ferroelectric, guest-host, phase change or surface stabilized or polymer stabilized cholesteric texture (SSCT, PSCT) displays, in optical elements, like reflective polarizers, retardation films, compensators, colour filters or holographic elements, especially in reflective films with patterned optical properties, in adhesives, synthetic resins with anisotropic mechanical properties, cosmetic and pharmaceutical compositions, diagnostics, liquid crystal pigments, for decorative and security applications, especially in security markings that are applied to items or documents of value for easy identification or prevention of falsification, in nonlinear optics, optical recording or information storage, or as chiral dopants.
  • optical elements like reflective polarizers, retardation films, compensators, colour filters or holographic elements, especially in reflective films with patterned optical properties, in adhesives, synthetic resins with anisotropic mechanical properties,
  • Another object of the invention is an anisotropic polymer film comprising a compound of formula I.
  • Another object of the invention is a reflective polymer film with patterned optical properties comprising a compound of formula I, in particular a cholesteric polymer film having different regions with different reflection wavelength.
  • Another object of the invention is a broadband reflective polarizer or colour filter comprising a compound of formula I.
  • Another object of the invention is a liquid crystal display comprising a liquid crystalline mixture or a polymerizable liquid crystalline mixture comprising at least one chiral compound of formula I.
  • Another object of the invention is a liquid crystal display comprising an optical component, in particular a broadband reflective polarizer or colour filter, comprising a compound of formula I.
  • inventive chiral photoisomerizable compounds are mesogenic or liquid crystalline, i.e. they can induce or enhance mesophase behaviour for example in a mixture with other compounds or exhibit one or more mesophases themselves. It is also possible that the inventive compounds show mesophase behaviour only in mixtures with other compounds, or, in case of polymerizable compounds, when being (co)polymerized. Mesogenic inventive compounds are especially preferred.
  • the compounds of formula I comprise one or more polymerizable groups.
  • compounds of formula I comprising one to four, in particular one or two photoisomerizable groups PI.
  • X 1 to X 6 are selected from the groups as defined in a).
  • these groups are selected from H, alkyl, alkenyl, alkoxy, alkenyloxy, alkylcarbonyl or alkylcarbonyloxy with 1 to 12 C-atoms that is optionally fluorinated, or have one of the meanings of P.
  • X 1 to X 6 are —B-(Sp) n -G, wherein B is a linkage group, Sp a spacer group and G a cyclic group as defined in formula I, and n is 0 or 1.
  • B is preferably —O—, —COO—, —O—COO— or a single bond, very preferably —COO— or a single bond, and n is preferably 0.
  • the cyclic group G is preferably selected from cyclobutane, cyclo-pentane, 3-(1,1,-dimethylcyclopentane), 2-tetrahydrofuran, 1-pyrrolidine, 2-furan, 2-pyrrol, 2-thiophene, 2-oxazole, 2-thiazole, 2-imidazole, 3-pyrrolidin-2-one, cyclohexane, 1-cyclohexene, 2-tetrahydropyran, 1-piperidine, 3-tetrahydrothiopyrane, 4-(1,3-dioxane), 1,4-dioxane, 2-(1,3,-dithiane), 1,4-dithiane, 2-oxathiane, 4-thiomorpholine, 4-morpholine, phenylene, 2-pyridine, 2-pyrimidine, 2-pyrazine, 4-bicyclohexane, 4′-bicyclohexyl-2-ene, 1-cyclohexane-1,4-dione
  • R having the meaning of formula I and s being 0, 1, 2, 3, 4 or 5.
  • X 1 to X 6 denote H, cyclohexyl, phenyl that is optionally substituted with 1 to 4 groups L as defined in formula II, or —(COO) o —S with o being 0 or 1 and S being alkyl with 1 to 4 C atoms.
  • X 1 to X 6 in particular the groups X 1 and X 6 or the groups X 2 and X 5 or the groups X 3 and X 4 are cyclohexyl or phenyl that is optionally substituted with 1 or 2 groups L as defined in formula II.
  • X 1 to X 6 is H and one of X 1 to X 6 is cyclohexyl, phenyl that is optionally substituted with 1 to 4 groups L as defined in formula II, or —(COO) o —S with o being 0 or 1 and S being alkyl with 1 to 4 C atoms, in particular those wherein one of X 1 and X 6 or one of X 2 and X 5 or one of X 3 and X 4 is H and the other is cyclohexyl, phenyl or —(COO) o —S.
  • two substituents X 7 or X 8 in neighboured positions on a phenyl ring can also form a fused carbocyclic or heterocyclic aliphatic or aromatic group with up to 25 C atoms, like for example in the following compounds
  • aromatic rings may also be mono- or polysubstituted with R as defined in formula I.
  • X 1 to X 6 denote —B-(Sp) n -(M 1 -Z 1 ) i -(PI) k -(Z 2 -M 2 ) i —R.
  • Very preferred compounds of this type are those wherein two of X 1 to X 6 , in particular the groups X 1 and X 6 or the groups X 1 and X 5 denote —B-(Sp) n -(M 1 -Z 1 ) i -(PI) k -(Z 2 -M 2 ) i —R, especially those wherein the two groups —B—(Sp) n -(M 1 -Z 1 ) i -(PI) k -(Z 2 -M 2 ) i —R are identical.
  • the compounds of formula I comprise at least one mesogenic group, which can be a photoisomerizable group PI that is in addition mesogenic, or a separate mesogenic group M 1 or M 2 .
  • the mesogenic groups M 1 and M 2 are preferably of formula II —(A 1 -Z) m -A 2 - II wherein
  • a 1 and/or A 2 can have one of the above meanings of G.
  • the mesogenic groups M 1 and/or M 2 preferably incorporate two or three five- or six-membered rings.
  • a smaller group of preferred mesogenic groups of formula II is listed below.
  • Phe in these groups is 1,4-phenylene that may also be substituted with 1 to 4 groups L as defined in formula II, Cyc is 1,4-cyclohexylene and Z has one of the meanings of formula II.
  • subformulae II-1, II-2, II-3, II-4, II-5, II-7 and II-10 are particularly preferred.
  • Z is preferably —COO—, —OCO—, —CH 2 CH 2 — or a single bond.
  • mesogenic groups M 1 and M 2 are selected from the following formulae and their mirror images
  • L and r have the above meanings, and r is preferably 0, 1 or 2.
  • subformulae IId, IIg, IIh, IIi, IIk and IIo are particularly preferred.
  • L is preferably F, Cl, CN, NO 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , OCF 3 , OCHF 2 or OC 2 F 5 , in particular F, Cl, CN, CH 3 , C 2 H 5 , OCH 3 , COCH 3 , CF 3 or OCF 3 , most preferably F, Cl, CH 3 , OCH 3 or OCF 3 .
  • the compounds of formula I comprise at least one photoisomerizable group PI.
  • the photoisomerizable group PI can be every group that is known to the skilled in the art for this purpose, as for example disclosed in John C. Coyle, “Introduction to Organo Photochemistry” 1986, John Wiley ans Sons, Chichester, UK.
  • C 1 and C 2 have independently of each other one of the meanings of A 1 as defined in formula II, and D 1 and D 2 are independently of each other CH or N. Further preferred are compounds wherein C 1 is a single bond.
  • D 1 and D 2 denote CH. Further preferred are compounds wherein D 1 and D 2 denote N.
  • PI is selected from the following formulae
  • D 1 and D 2 are CH or N
  • L has the meaning of formula II
  • r has the meaning given above.
  • groups IIId especially those wherein D 1 and D 2 are CH.
  • R 1 , R 2 , Z, A 1 , A 2 , a and b have the meanings given above, in particular those wherein a and b are 0 and R 1 and R 2 are P-Sp.
  • R in formula I is an alkyl or alkoxy radical, i.e. where the terminal CH 2 group is replaced by —O—, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
  • straight chain alkyl or alkoxy with 1 to 8 C atoms is especially preferred.
  • R in formula I can be a polar or an unpolar group.
  • a polar group it is preferably selected from CN, NO 2 , halogen, OCH 3 , SCN, COR 8 , COOR 8 or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms.
  • R 8 is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms.
  • polar groups are selected of F, Cl, CN, NO 2 , OCH 3 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , C 2 F 5 , OCF 3 , OCHF 2 , and OC 2 F 5 , in particular of F, Cl, CN, OCH 3 and OCF 3 .
  • an unpolar group it is preferably alkyl with up to 15 C atoms or alkoxy with 2 to 15 C atoms.
  • R in formula I can be an achiral or a chiral group.
  • a chiral group it is preferably selected according to formula IV:
  • the O atom is preferably adjacent to the chiral C atom.
  • Preferred chiral groups are 2-alkyl, 2-alkoxy, 2-methylalkyl, 2-methylalkoxy, 2-fluoroalkyl, 2-fluoroalkoxy, 2-(2-ethin)-alkyl, 2-(2-ethin)-alkoxy, 1,1,1-trifluoro-2-alkyl and 1,1,1-trifluoro-2-alkoxy.
  • achiral branched groups of this type generally do not contain more than one chain branch.
  • Another preferred embodiment of the present invention relates to compounds of formula I wherein R is denoting P-(Sp) n .
  • R 0 in formula I is preferably H or CH 3 , in particular H.
  • the polymerisable group P is preferably selected from CH 2 ⁇ CW 1 —COO—
  • P is particularly preferably an acrylate, methacrylate, vinyl, vinyloxy, epoxy, styrene or propenyl ether group, in particular an acrylate, methacrylate, vinyl or epoxy group.
  • Sp is preferably a straight chain or branched alkylene group having 1 to 20 C atoms, in particular 1 to 12 C atoms, in which, in addition, one or more non-adjacent CH 2 groups may be replaced by —O—, —S—, —NR 0 —, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)—, —CH(CN)—, —CH(OH)—, —(CF 2 ) x —, —(CD 2 ) x —, —CH ⁇ CH—, —CF ⁇ CF—, —CH ⁇ CF— or —C ⁇ C—, with x being an integer from 1 to 12, and in which one or more H atoms may be replaced by halogen, CN or OH.
  • Typical spacer groups are for example —(CH 2 ) y , —(CH 2 CH 2 O) z —CH 2 CH 2 —, —CH 2 CH 2 —S—CH 2 CH 2 — or —CH 2 CH 2 —NH—CH 2 CH 2 —, with y being an integer from 2 to 12 and p being an integer from 1 to 3.
  • Preferred spacer groups are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene for example.
  • Straight-chain groups are especially preferred.
  • the O atom is preferably adjacent to the chiral C atom.
  • halogen is preferably F or Cl.
  • inventive chiral compounds can be synthesized according to or in analogy to methods which are known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for said reactions. Use may also be made here of variants which are known per se, but are not mentioned here. Further methods for preparing the inventive compounds can be taken from the examples.
  • inventive compounds can be prepared according to or in analogy to the following reaction schemes.
  • DCC 4-(dimethylamino)-pyridine, DCM, r.t.
  • DCC 4-(dimethylamino)-pyridine, DCM, r.t.
  • NEt 3 35° C.
  • the inventive chiral compounds can be used in a liquid crystal mixture for liquid crystal displays exhibiting a twisted molecular structure of the liquid crystal matrix like, for example, twisted or supertwisted nematic displays with multiplex or active matrix addressing, or in displays comprising a liquid crystal mixture with a chiral liquid crystalline phase, like for example chiral smectic or chiral nematic (cholesteric) mixtures for ferroelectric or cholesteric displays.
  • inventive compounds, mixtures and polymers are especially suitable for cholesteric displays, like for example surface stabilized or polymer stabilized cholesteric texture displays (SSCT, PSCT) as described in WO 92/19695, WO 93/23496, U.S. Pat. No. 5,453,863 or U.S. Pat. No. 5,493,430, in particular for liquid crystal devices with variable pitch, like multi-domain liquid crystal displays as described for example in WO 98/57223, or multicolour cholesteric displays as described for example in U.S. Pat. No. 5,668,614.
  • SSCT surface stabilized or polymer stabilized cholesteric texture displays
  • inventive compounds of formula I are also suitable for use in photochromic liquid crystal media, which change their colour upon photoradiation.
  • Another object of the invention is a liquid crystalline mixture comprising at least one chiral compound of formula I.
  • Yet another object of the invention are cholesteric liquid crystal displays comprising cholesteric liquid crystalline media containing at least one chiral compound of formula I.
  • inventive compounds are characterized by a good solubility in liquid crystalline host mixtures, and can be added as dopants to liquid crystalline hosts in high amounts without significantly affecting the phase behaviour and electrooptical properties of the mixture. Undesired spontaneous crystallization at low temperatures is thereby reduced and the operating temperature range of the mixture can be broadened. Furthermore, these chiral compounds can be used for the preparation of a highly twisted liquid crystal medium even if they have a low HTP, because the dopant concentration can be increased to yield low pitch values (i.e. high twist) without affecting the mixture properties. The use of a second dopant, which is often added to avoid crystallization, can thus be avoided.
  • inventive chiral compounds of formula I exhibit high values of the HTP.
  • a liquid crystalline mixture with high helical twist i.e. a low pitch, can be prepared by using these compounds as dopants, or a liquid crystalline mixture with moderate helical twist can be achieved by using these inventive compounds as dopants already in very small amounts.
  • inventive compounds are furthermore advantageous because they are affecting the physical properti s of the liquid crystalline mixture only to a minor extent.
  • a liquid crystalline mixture according to the invention comprises preferably 0.1 to 30%, in particular 1 to 25% and very particularly preferably 2 to 15% by weight of chiral compounds of formula I.
  • a liquid crystalline mixture according to the invention preferably comprises 1 to 3 chiral compounds of formula I.
  • the liquid crystalline mixture is consisting of 2 to 25, preferably 3 to 15 compounds, at least one of which is a chiral compound of formula I.
  • the other compounds are preferably low molecular weight liquid crystalline compounds selected from nematic or nematogenic substances, for example from the known classes of the azoxybenzenes, benzylidene-anilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohehexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid and of cyclohex
  • the liquid crystalline mixture of this preferred embodiment is based on the achiral compounds of this type.
  • G′ in these compounds is selected from the following bivalent groups —CH ⁇ CH—, —N(O)N—, —CH ⁇ CY—, —CH ⁇ N(O)—, —C ⁇ C—, —CH 2 —CH 2 —, —CO—O—, —CH 2 —O—, —CO—S—, —CH 2 —S—, —CH ⁇ N—, —COO-Phe-COO— or a single bond, with Y being halogen, preferably chlorine, or —CN.
  • R′ and R′′ are, in each case, independently of one another, alkyl, alkenyl, alkoxy, alkenyloxy, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy with 1 to 18, preferably 3 to 12 C atoms, or alternatively one of R′ and R′′ is F, CF 3 , OCF 3 , Cl, NCS or CN.
  • R′ and R′′ are, in each case, independently of each another, alkyl, alkenyl or alkoxy with different chain length, wherein the sum of C atoms in nematic media generally is between 2 and 9, preferably between 2 and 7.
  • a preferred use of the inventive compounds is the preparation of polymerizable liquid crystalline mixtures, anisotropic polymer gels and anisotropic polymer films, in particular polymer films that exhibit a helically twisted molecular structure with uniform planar orientation, i.e. wherein the helical axis is oriented perpendicular to the plane of the film, like oriented cholesteric films.
  • Anisotropic polymer gels and displays comprising them are disclosed for example in DE 195 04 224 and GB 2 279 659.
  • Oriented cholesteric polymer films can be used for example as broadband reflective polarizers, colour filters, security markings, or for the preparation of liquid crystal pigments.
  • Broadband cholesteric reflective polarizers are described for example in EP 0 606 940, WO 97/35219 or EP 0 982 605.
  • Colour filters are described for example in EP 0 720 041 or EP 0 685 749 and R.
  • Liquid crystal pigments are described for example in EP 0 601 483, WO 97/27251, WO 97/27252, WO 97/30136 or WO 99/11719.
  • the liquid crystalline mixture should comprise at least one polymerizable compound, preferably a polymerizable mesogenic compound.
  • Another object of the invention are polymerizable liquid crystalline mixtures comprising at least two compounds, at least one of which is a chiral compound of formula I and at least one of which is a polymerizable compound.
  • the polymerizable compound can be said at least one compound of formula I or an additional compound.
  • polymerizable mesogenic compounds that can be used as co-components in the polymerizable mixture are disclosed for example in WO 93/22397; EP 0,261,712; DE 195,04,224; WO 95/22586 and WO 97/00600.
  • the polymerizable mixture comprises at least one polymerizable mesogenic compound having one polymerizable functional group and at least one polymerizable mesogenic compound having two or more polymerizable functional groups.
  • x is an integer from 1 to 12
  • A is 1,4-phenylene or 1,4-cyclohexylene
  • v is 0 or 1
  • Y 0 is a polar group
  • R 7 is an unpolar alkyl or alkoxy group
  • Ter is a terpenoid radical like e.g. menthyl
  • Chol is a cholesteryl group
  • L 1 and L 2 are each independently H, F, Cl, CN, OH, NO 2 or an optionally halogenated alkyl, alkoxy or carbonyl group with 1 to 7 C atoms.
  • the polar group Y 0 is preferably CN, NO 2 , halogen, OCH 3 , OCN, SCN, COR 8 , COOR 8 or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms.
  • R 8 is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms.
  • the polar group Y 0 is selected of F,Cl, CN, NO 2 , OCH 3 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , C 2 F 5 , OCF 3 , OCHF 2 , and OC 2 F 5 , in particular F, Cl, CN, OCH 3 and OCF 3 .
  • the unpolar group R 7 is preferably an alkyl group with 1 or more, preferably 1 to 15 C atoms or an alkoxy group with 2 or more, preferably 2 to 15 C atoms.
  • the mono- and difunctional polymerizable mesogenic compounds of above formulae VI and VII can be prepared by methods which are known per se and which are described in the documents cited above and, for example, in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the polymerizable liquid crystalline mixtures comprise at least one inventive chiral compound of formula I, at least one monofunctional compound of formulae VIa–VIm and at least one bifunctional polymerizable compound of formulae VIIa–VIIe.
  • polymerizable liquid crystalline mixtures comprise at least one inventive chiral compound and at least two monofunctional compounds of formulae VIa–VIm.
  • Another object of the invention is an anisotropic polymer film with an oriented chiral liquid crystalline phase obtainable by (co)polymerizing a liquid crystalline mixture comprising at least one chiral compound of formula I and at least one polymerizable mesogenic compound preferably selected of formula VIa–VIm and VIIa–VIIe and/or at least one polymerizable chiral compound of formula I.
  • the preparation of an anisotropic polymer film with twisted structure from a polymerizable mixture is generally described for example in D. J. Broer, et al., Angew. Makromol. Chem. 183, (1990), 45–66.
  • the cholesteric polymerizable mixture is coated onto a substrate, aligned into uniform planar orientation, and polymerized in situ by exposure to heat or actinic radiation, thereby fixing the uniform alignment. Alignment and curing are carried out in the chiral liquid crystalline phase of the polymerizable mixture.
  • Actinic radiation means irradiation with light, like UV light, IR light or visible light, irradiation with X-rays or gamma rays or irradiation with high energy particles, such as ions or electrons.
  • a source for actinic radiation for example a single UV lamp or a set of UV lamps can be used.
  • Another possible source for actinic radiation is a laser, like e.g. a UV laser, an IR laser or a visible laser.
  • a photoinitiator when photopolymerizing by means of UV light, a photoinitiator can be used that decomposes under UV irradiation to produce free radicals or ions that start the polymerization reaction. It is also possible to use a cationic photoinitiator, when curing reactive mesogens with for example vinyl and epoxide reactive groups, that photocures with cations instead of free radicals.
  • the commercially available Irgacure 651, Irgacure 184, Darocure 1173 or Darocure 4205 can be used, whereas in case of cationic photopolymerization the commercially available UVI 6974 (Union Carbide) can be used.
  • the polymerizable liquid crystalline mixtures comprising polymerizable chiral compounds of formula I and/or polymerizable mesogenic compounds of formulae VI and VII additionally comprise 0.01 to 10%, in particular 0.05 to 8%, very preferably 0.1 to 5% by weight of a photoinitiator, especially preferably a UV-photoinitiator.
  • polymerization is carried out under an atmosphere of inert gas, preferably under a nitrogen atmosphere.
  • a substrate for example a glass or quarz sheet as well as a plastic film or sheet can be used. It is also possible to put a second substrate on top of the coated mixture prior to, during and/or after polymerization.
  • the substrates can be removed after polymerization or not.
  • at least one substrate has to be transmissive for the actinic radiation used for the polymerization. Isotropic or birefringent substrates can be used.
  • the substrate is not removed from the polymerized film after polymerization, preferably isotropic substrates are used.
  • a plastic substrate such as for example a film of polyester such as polyethyleneterephthalate (PET), of polyvinylalcohol (PVA), polycarbonate (PC) or triacetylcellulose (TAC), especially preferably a PET film or a TAC film.
  • PET films are commercially available from ICI Corp. under the trade name Melinex.
  • the polymerizable mixture is preferably coated as a thin layer on a substrate or between substrate, and aligned in its chiral mesophase, e.g. the cholesteric or chiral smectic phase, to give a planar orientation, i.e. wherein the axis of the molecular helix extends transversely to the layer.
  • Planar orientation can be achieved for example by shearing the mixture, e.g. by means of a doctor blade.
  • an alignment layer for example a layer of rubbed polyimide or sputtered SiO x , on top of at least one of the substrates.
  • a second substrate is put on top of the coated material. In this case, the shearing caused by putting together the two substrates is sufficient to give good alignment.
  • an electric or magnetic field to the coated mixture.
  • a second substrate not only to aid alignment of the polymerizable mixture but also to exclude oxygen that may inhibit the polymerization.
  • curing can be carried out under an atmosphere of inert gas.
  • curing in air is also possible using suitable photoinitiators and high lamp power.
  • oxygen exclusion most often is not needed, but water should be excluded.
  • An inventive polymerizable liquid crystalline mixture for the preparation of anisotropic polymer films comprises preferably 0.1 to 35%, in particular 0.5 to 15% and very particularly preferably 0.5 to 5% by weight of one or more polymerizable chiral compounds of formula I.
  • Polymerizable liquid crystalline mixtures are preferred that comprise 1 to 3 chiral compounds of formula I.
  • inventive polymerizable liquid crystalline mixtures can additionally comprise one or more other suitable components such as, for example, catalysts, sensitizers, stabilizers, inhibitors, co-reacting monomers, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes or pigments.
  • suitable components such as, for example, catalysts, sensitizers, stabilizers, inhibitors, co-reacting monomers, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes or pigments.
  • the inventive polymerizable mixture comprises a stabilizer that is used to prevent undesired spontaneous polymerization for example during storage of the composition.
  • a stabilizer in principal all compounds can be used that are known to the skilled in the art for this purpose. These compounds are commercially available in a broad variety. Typical examples for stabilizers are 4-ethoxyphenol or butylated hydroxytoluene (BHT).
  • non mesogenic compound with two or more polymerizable functional groups preferably in an amount of up to 20% by weight
  • Typical examples for difunctional non mesogenic monomers are alkyldiacrylates or alkyldimethacrylates with alkyl groups of 1 to 20 C atoms.
  • Typical examples for non mesogenic monomers with more than two polymerizable groups are trimethylpropanetrimethacrylate or pentaerythritoltetraacrylate.
  • inventive compositions comprising compounds with only one polymerizable functional group leads to linear polymers, whereas in the presence of compounds with more than one polymerizable functional group crosslinked polymers are obtained.
  • liquid crystalline mixtures can be polymerized in situ as described above, however, in this case alignment of the polymerizable mixture is not always necessary.
  • Photoirradiation can be achieved for example with irradiation by UV light or other high energy sources such as lasers.
  • the photoisomerizable compounds of formula I are particularly suitable for the preparation of cholesteric films or layers with planar alignment. Such layers or films show selective reflection of visible light that is circularly polarized, caused by interaction of incident light with the helically twisted structure of the cholesteric material.
  • the inventive compounds and mixtures can for example be used to prepare reflective cholesteric films wherein the optical properties, like the reflection wavelength ⁇ and the reflection bandwidth ⁇ , can be varied easily.
  • cholesteric reflective films with a horizontal pattern comprising regions of different reflection wavelength ⁇ , or broadband reflective films with a broad bandwidth ⁇ of the reflected wavelength band can be prepared.
  • the preparation of such films is described for example in WO 00/34808 and in P. van de Witte et al., J. Mater. Chem. 9 (1999), 2087–2094, the entire disclosure of which is incorporated into this application by way of reference.
  • the preparation of patterned cholesteric films and of broadband reflective films is also exemplarily described below.
  • a cholesteric film with variable wavelength can for example be prepared as follows:
  • a thin layer of a cholesteric polymerizable mixture comprising an inventive chiral photoisomerizable compound of formula I is coated onto a substrate and aligned into planar orientation as described above.
  • the coated and aligned layer shows selective reflection of a wavelength ⁇ that is depending on the helical pitch p according to above equation (2). If the coated layer is exposed to photoradiation of a suitable wavelength, the photoisomerizable group(s) in the compound of formula I is isomerized.
  • the compound of formula I comprises a photoisomerizable group PI of formula IIIa wherein D 1 and D are CH (stilbene group)
  • the stilbene group will undergo E-Z-isomerization if the wavelength of radiation is selected accordingly between 300 and 400 nm.
  • the degree of isomerization and the shift of ⁇ can be controlled by varying e.g. the irradiation time and/or the radiation dose.
  • the structure of the layer is then fixed by in-situ polymerization.
  • the helical pitch and reflection wavelength will change only in th exposed parts, but remain unchanged in the non-exposed parts. This can be achieved for example by photoradiation through a photomask that is applied on top of the coated layer. Afterwards, the cholesteric structure is fixed in those parts where the pitch has changed by polymerization, for example by in-situ photopolymerization through the photomask. If the above steps of photoisomerization and (photo)polymerization are then repeated for the previously non-exposed parts of the coated layer under different conditions, e.g. different irradiation time and/or radiation dose, a patterned cholesteric film is obtained with different regions showing different reflection wavelengths.
  • Such patterned films are suitable for example for use as colour filter in optical or electrooptical devices like liquid crystal displays or projectors. They can also be used for security markings, e.g. to identify or prevent falsification of credit cards, passports, bank notes or other documents of value.
  • a broadband reflective cholesteric film can for example be prepared as follows:
  • a layer of a cholesteric mixture with planar orientation comprising a photoisomerizable compound of formula I additionally comprises a dye having an absorption maximum at the wavelength where the isomerizable compound shows photoisomerization.
  • the mixture may comprise an isomerizable compound showing isomerization at a wavelength in the UV range together with a UV dye. If the mixture is exposed to UV radiation as described above, the dye will create a gradient in UV light intensity throughout the thickness of the layer. As a consequence, the isomerization is faster at the top of the layer than at the bottom and a pitch gradient is created, leading to a broadening of the reflected wavelength band.
  • the pitch gradient and reflection bandwidth can be controlled for example by varying the film thickness, irradiation time, radiation dose and/or the concentration of the UV dye and the photoisomerizable compound. If the cholesteric mixture comprises one or more polymerizable components, the structure of the film can be fixed by in-situ polymerization.
  • HTP values of the examples were determined in the commercially available liquid crystal host mixture MLC-6260 (Merck KGaA, Darmstadt, Germany) at a concentration of 1% and a temperature of 20° C.
  • “Conventional workup” means: water is added if necessary, the mixure is extracted with methylene chloride, diethyl ether or toluene, the phases are separated, the organic phase is dried and concentrated by evaporation, and the product is purified by crystallization and/or chromatography.
  • the polymerizable mixture M was formulated, comprising
  • FX13® is a polymerizable nonionic surfactant with a perfluoroalkyl group which is commercially available from 3M Corp.
  • TPO 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, Trademark Lucirin® TPO
  • BASF AG BASF AG
  • Mixture M is dissolved in xylene to give solution S1 with a concentration of 50% of total solids. 0.0395 g of compound (1) of example 1 are added to 0.9566 g of solution S1 to give solution S2 with the concentration of (1) being 7.94% of total solids.
  • Thin films of the solution S2 are coated onto a substrate and isomerized in air for different periods of time, using 3.8 mW/cm ⁇ 2 radiation from a medium pressure Hg lamp. Immediately after isomerization each film was polymerized using approx. 15 mW/cm ⁇ 2 radiation from the same medium Hg pressure lamp in an N 2 atmosphere. In this way, the following polymer films are obtained
  • FIG. 1 The reflection spectrum of the polymer films P1–P5 are depicted in FIG. 1 . It can be seen that the central wavelength of reflection is shifted towards higher values with increasing isomerization time.
  • FIG. 2 depicts the central wavelength of reflection of films P1–P5 versus isomerization time.

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US7435357B2 (en) * 2003-04-08 2008-10-14 Merck Patent Gmbh Polymerised liquid crystal film with retardation or orientation pattern
US20060193998A1 (en) * 2003-04-08 2006-08-31 Richard Harding Polymerised liquid crystal film with retardation or orientation pattern
US20100052196A1 (en) * 2006-01-27 2010-03-04 Fujifilm Corporation Optically driven actuator and method of manufacturing the same
US20100134736A1 (en) * 2008-12-01 2010-06-03 Chunghwa Picture Tubes, Ltd. Liquid crystal material and optical compensated bend mode liquid crystal display
US7771618B2 (en) 2008-12-01 2010-08-10 Chunghwa Picture Tubes, Ltd. Liquid crystal material and optical compensated bend mode liquid crystal display
US20110061670A1 (en) * 2009-03-11 2011-03-17 Kent Displays Incorporated Color changing artificial fingernails
US8176924B2 (en) * 2009-03-11 2012-05-15 Kent Displays Incorporated Color changing artificial fingernails
US8540896B2 (en) 2009-11-12 2013-09-24 Industrial Technology Research Institute Chiral compound and liquid crystal composition containing the same
US20110109868A1 (en) * 2009-11-12 2011-05-12 Industrial Technology Research Institute Chiral compound and liquid crystal composition containing the same
US20120035293A1 (en) * 2010-07-07 2012-02-09 Boydston Andrew J On-demand photoinitiated polymerization
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US8933143B2 (en) * 2010-07-07 2015-01-13 California Institute Of Technology On-demand photoinitiated polymerization
US8481129B2 (en) 2011-11-25 2013-07-09 Industrial Technology Research Institute Liquid crystal compounds, and liquid crystal displays and photochromic materials comprising the liquid crystal compounds
US10774059B2 (en) 2016-12-19 2020-09-15 Cellix Bio Private Limited Compositions and methods for the treatment of inflammation
US11266495B2 (en) 2019-10-20 2022-03-08 Rxsight, Inc. Light adjustable intraocular lens with a modulable absorption front protection layer
WO2022120120A1 (en) * 2020-12-03 2022-06-09 The Regents Of The University Of California Devices comprising a liquid crystal layer and uses thereof

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